Graft copolymers comprised of certain monomeric diacrylic esters of polyglycols on nu-vinyl-3-morpholinone polymer substrates, improved acrylonitrile polymer compositions obtainable therewith, and method of preparation



United States Patent Ofiice 3,926,295 Patented Mar. 20, 1962 GRAFTCQPGLYMERS COMPRISED OF CERTAIN MONGMERZC DEACRYLIC ESTERS F PCLY-GLYCOLS ON N ViN YL 3 MORPHQLINONE POLYMER SUBSTRATES, IMPROVED ACRYLG-NTI'RILE POLYMER COMPOSITIONS OBTAIN- ABLE THEREWITH, AND METHOD {BFPREP- ARATION Stanley A. Murdock, Concord, Calif, and Ardy Arm-en,

Denbigh, Va., assignors to The Dow Chemical Company, Midland, Mich acorporation of Delaware Filed Dec. 3, 1959, Ser. No. 357,163 17 Claims.(Cl. 260-455) The present invention resides in the general field oforganic chemistry and contributes specifically to the polymer art,especially with respect to certain cross-linked, water-insoluble graftcopolymer compositions and fiberforming polymer blends obtainabletherewith. It is particularly concerned with graft copolymers of certainpolyfunctional monomeric diacrylate and dimethacrylate esters ofpolyglycols on or with preformed substrate or backboneN-vinyl-3-morpholinone polymers (hereinafter referred to as VMpolymers). Such graft copolymeric products have especial utility asdye-receptive, antistatic and stabilizing additaments for acrylonitrilepolymer compositions which, advantageously, may be of the fiber-formingvariety.

The invention is thus also concerned with the compositions that may beobtained by blending the graft copolymers with acrylonitrile polymers,as well as with shaped articles which have been fabricated from suchcompositions and which, as a consequence, have significantly enhancedproperties and characteristics as regards improvements in and relatingto enhanced dye-receptivity, minimized inherent propensity to accumulateelectrostatic charges, natural stability to various deterioratinginfluences, including stability against becoming deleteriouslyinfluenced and degraded upon exposure to heat at elevated temperaturesand to light.

Within the scope and purview of the invention, there are comprehended(1) the various novel and utile graft copolymers of therindicatedvariety; (2) the advantageous polymer compostions, particularlyfiber-forming compositions, obtained by blending the graft copolymerswith acrylonitrile polymers; (3) various shaped articles fabricated fromand comprised of the graft copolymer-conraining acrylonitrile polymercompositions; and (4) methods for the preparation of the above-indicatedcompositions.

It is the main purpose and primary design of the present invention toprovide and make available graft copolymers of certain monomericdiacrylate and dimethacrylate esters of polyglycols on V M polymersubstrates or backbones, which graft copolymer products are especiallywell suited for being incorporated in acrylonitrile polymercompositions, particularly compositions of polyacrylonitrile, to servein the indicated treble capacity of dye-assisting adjuvants, antistaticagents and stabilizing ingredients.

It is also a principal aim and chief concern of the invention to provideand make available acrylonitrile polymer compositions and shapedarticles therefrom that contain the above-indicated and hereinafter morefully delineated type of graft copolymeric additaments whichcompositions have, as intrinsic distinguishing characteristics,excellent receptivity of and acceptability for any of a wide variety ofdyestuffs; permanently imbued antistatic properties that are unusuallygood for and not commonly encountered in polymeric materials of suchsubstances; and eificacious natural stability to heat and light, as wellas to certain chemical conditions, such as alkaline environments.

The graft copolymers of the present invention which have the indicatedcapacity and utility as additaments for acrylonitrile polymercompositions are comprised of (b) a preformed VM polymer trunk or basesubstrate upon which there is graft copolymerized a (a) diacrylate ordimethacrylate ester of certain polyglycols or their mixtures, ashereinafter more fully illustrated. Advantageously, in many instances,the graft copolymers of the present invention may be comprised of mixedgraft substituents from diverse monomers, a portion of such graftsubstituents being derived from (1) the diacrylate or dimethacrylateesters of polyglycols and the remainder being graft copolymerizedsubstituents on the VM polymer substrate of (2) certain monomeric,alkenyl groupcontaining organic sulfonic acid compounds, or theirderivatives, which monomeric organic sulfonic acid compounds arehereinafter more fully delineated.

The polymer blend compositions of the present invention which fulfillthe above-indicated ends and offer corollary advantages and benefits,particularly as fiber-forming compositions as will hereinafter bemanifest, are, in essence, comprised of an intimate and practicallyinseparable blend or alloy constitution of (A) an acrylonitrile polymerthat contains in the polymer molecule at least about Weight percent ofpolymerized acrylonitrile, any balance being copolymerized units of atleast one other ethylenically unsaturated monomeric material that iscopolymerizable with acrylonitrile to provide fiber-formingacrylonitrile polymer products which acrylonitrile polymer is preferablyof the fiber-forming variety and, most advantageously, ispolyacrylonitrile and (B) a minor proportion of the above-indicatedvariety of beneficial graft copolymeric additament that functions in thedescribed manner.

The methods of the invention by which the herein contemplatedadvantageous compositions may be made involve preparation of the graftcopolymers, as Well as incorporation of a minor proportion of the graftcopolymer products as a beneficial additament in and with anacrylonitrile polymer base by any of several beneficial techniques,hereinafter more thoroughly defined, adapted to suitably accomplish thedesired result.

Without being limited to or by the specific embodiments and modes ofoperation set forth, the invention is exemplified in and by thefollowing didactic illustrations wherein, unless otherwise indicated,all parts and percentages are to be taken on a weight basis.

ILLUSTRATION A Into a 50-0 ml., 3 neck, round bottom flask that isequipped with an efiicient agitator, a nitrogen sparger andfractionating column, there is charged about grams of a polyglycol(having a molecular weight of about 600) and of the general structuralformula: HO(CH CH O) CH CH OH; 134 grams of methyl methacrylate; 5 gramsof para-toluene sulfonic acid; and about 6.7 grams of polymerizationinhibiting hydroquinone. The mixture of charged ingredients in thereactor is brought to the boil and maintained at that temperature withthe fractionating column set at total reflux until the overheadtemperature reaches about 64-65 C. When this temperature is attained,the overhead azeotrope of methanol and methyl methacrylate is removedfor a period of about 6 hours at a temperature of 65 to 67 C. After this6-hour period, the overhead temperature increases to about 80 C. Thereaction is then terminated by removal of the heat source.

The excess methyl methacrylate is then removed from the reaction mass byvacuum distillation. About 1 liter of water is then added to thereaction mass and the solid polymer particles that are formed thereinare removed 3 by filtration. The aqueous solution of the polyglycol typemonomer that remains is then passed through an ion exchange bedconsisting of an anionic quaternary ammonium type resin (Dowex-l) toremove the hydroquinone. The uninhibited monomer solution is then storedat a temperature of about 30 C.

About 2.1 grams of the prepared monomeric diester is then charged toanother reactor which is equipped with agitating means, a nitrogensparger, and a total reflux condenser. There is also charged into thesecond reactor about 4.9 grams of pcly-N-vinyl-3-morpholinone (PVM);28.3 grams of water and 0.04 gram of potassium persulfate. The relativeviscosity of the PVM in water at 25 C. is about 1.85 at a concentrationof 1 gram of the water-soluble polymer in 100 m1. of solution. Theresulting solution is heated to a temperature of about 50 C. andsynthermally maintained thereat for a period of about 32 hours under anitrogen blanket. The reaction is then terminated and the graftcopolymer-containing solution is removed from the reactor.

The polymer product is a clear light brown solution that has a polymercontent of about 19.5 percent. Upon analysis, it is found that about 95percent of the diester monomer is converted to a graft copolymer productwith the PVM. The graft copolymer product contains about 29 percent ofthe graft copolymerized substituents and 71 percent of the PVM.

The graft copolymer is found to be an excellent additive for enhancingthe dye-receptivity of synthetic acrylonitrile polymer textile fibers(such as those based essentially on polyacrylonitrile) to many of a widevariety of dyestuffs; decreasing the propensity of such fibers toaccumulate charges of static electricity; and stabilizing the fiber tolight, heat and alkaline media when it is incorporated inpolyacrylonitrile in the manner set forth in the following example.

ILLUSTRATION B Following the procedure of Illustration A, and using thesame monomeric diester of the polyglycol as therein described, a graftcopolymeric additament is prepared from the following charge:

The charged ingredients, which have a pH of about 6 (after adjustmentwith hydrochloric acid), are maintained at a temperature of about 70 C.for 21 hours. During this time the mixture of the diester monomer andthe organic sulfonic acid monomer forms a mixed graft copolymer producton the PVM. Conversion of the monomers to graft copolymer product isfound to be about 91.3 percent. The graft copolymer product, which isobtained in the aqueous reaction mass as a slightly colored,water-insoluble gel, is found to contain about 72 percent of PVM, about23 percent of graft copolymerized diester units and about percent ofgraft copolymerized sodium styrene sulfonate units. A stable dispersionfor use in impregnating polyacrylonitrile aquagel fiber is made byputting the gel with additional water through a Waring Blendor so as toobtain an aqueous dispersion of the graft copolymer product containingabout 9.4 percent of dispersed polymer solids.

Polyacrylonitrile fibers containing about 11.8 percent of the abovecopolymer product are prepared by impregnating filamentary structuresthat arean aquagel condition (after having been salt-spun andwet-stretched) in and with a dissolved aqueous dispersion of the graftcopolymer product that contains about 1.5 percent of the graft copolymersolids. The polyacrylonitrile aquagel fiber is obtained by extruding aspinning solution of fiberforming polyacrylonitrile comprised of about10 parts of the polymer dissolved in parts of a 60 percent aqueoussolution of zinc chloride through a spinnerette having 750 individual 6mil diameter orifices into an aqueous coagulating bath that containsabout 42 percent of dissolved Zinc chloride to form a multiple filamenttow. After being spun, the tow bundle of coagulated polyacrylonitrileaquagel fiber is washed substantially free from salt upon beingwithdrawn from the coagulating bath and then wet-stretched fororientation to a total stretched length that is about thirteen times(13X) its original extruded length. The aquagel fiber is then passedthrough the mentioned aqueous impregnating bath of the dissolvedcopolymer additive so as to become impregnated therewith to theindicated extent.

Following the impregnation, the aquagel fiber is irreversibly dried atC. to destroy the water-hydrated structure and convert it to a finishedfiber form. It is then beat set for five minutes at 150 C. The finallyob tained 2.5 denier fiber product has a tenacity of about 4 grams perdenier, an elongation of about 28 percent, and a wet yield strength ofabout 0.95 gram per denier. The graft copolymer-containingacry-lonitrile polymer fiber product is found to have excellent naturalstability to heat and light as well as against becoming degraded unerthe influence of aqueous alkaline media at pH levels as high as 10. Itis found to be nearly free of propensity to accumulate charges of staticelectricity upon handling; being about commensurate with viscose rayonfibers in this regard. As is widely appreciated, viscose rayon is notconsidered to be aiflicted to a troublesome degree with problems due tostatic.

In addition, the graft copolymer-conta-ining sample has good color andhand and is dyeable with all classes of dyestufis as applied undernormal dyeing conditions.

The fiber product dyes well to deep and level shades of coloration withCalcodur Pink 2BL, a direct type of dyestuff (Colour Index Direct Red75, formerly Colour Index 353) and Sevron Brilliant Red 4G, a basic dyeformerly known as Basic Red 46 (Colour Index Basic Red 14).

The dyeing with Calcodur Pink 2BL is performed at the 4 percent levelaccording to conventional procedure in which the fiber sample ismaintained for about one hour at the boil in the dye bath which containsthe dyestufl in an amount equal to about 4 weight percent of the fiber(OWF), OWF designating on the dry weight of the fiber as defined in US.Patent No. 2,931,694. The dye bath also contains sodium sulfate (i.e.,Glaubers salt) in an amount equal to about 15 percent OWF and has abath-to-fiber weight ratio of about 30: 1, respectively. After beingdyed, the fiber is rinsed thoroughly with water and dried for about 20minutes at 80 C.

The dye-receptivity of the Calcodur Pink ZBL-dyed fiber is thenevaluated spectrophotometrically by measuring the amount ofmonochromatic light having a Wave length of about 520 millimicrons froma standard source that is reflected from the dyed sample. A numericalvalue on an arbitrarily designated scale from zero to one hundred isthereby obtained. This value represents the relative comparison of theamount of light that is reflected from a standard white tile reflectorthat has a reflectance value of 316 by extrapolation from the 0100scale. Lower reflectance values are an indication of betterdye-receptivity in the fiber. For example, a reflectance value of 50 orless is fairly good. A value as low as about 20 to 25 for acrylonitrilepolymer fibers dyed with 4 percent Calcodur Pink 2BL is generallyconsidered by those skilled in the art to be representative of a degreeof dye-receptivity that readily meets or exceeds the most rigorouspractical requirements and is ordinarily assured of receiving generalcommercial acceptance and approval.

The 4 percent Calcodur Pink 2BL reflectance value of thecopolymer-containing fiber product is about 18.

The antistatic properties of the graft copolymer-containing fiber arethen determined by measuring the electrical conductance of the fiberproduct at various humidities. As is also appreciated by those who areskilled in the art, the basis for such a test is that all fibers have atendency to generate static electricity upon being handled. Only thosethat are possessed of sufiicient electrical conductance to dissipate thecharge as quickly as it forms are not hampered by the bothersome effectsof static electricity. Thus, a measure of the electrical conductance ofa fiber is a good indication of its ability to dissipate staticelectricity. The conductivities of the various fiber samples tested arefound by determining their electrical resistances. Resistance, ofcourse, is the reciprocal quantity of conductivity. In order to permitvarious fiber samples to be compared on a common basis, theconductivities of the samples tested were actually measured as volumeresistivities according to the following formula:

Volume resistivity (Resistance)(cross-sectional area) Path lengthbetween electrodes to which sample being tested is attached The units ofvolume resistivity are ohrn-cm. /cm.

Prior to being tested, the graft copolymer-containing polyacrylonitrilefiber prepared in the indicated manner is vat dyed in the conventionalmanner with Cibanone Green BF Dbl. Paste (Colour Index Vat Green No. 1).A portion of the vat dyed sample is then subjected to five (5)consecutive No. 3-A accelerated Wash tests in accordance with theAmerican Association of Textile Chemists and Colorists (AATCC) Manual.The actual resistivity of the merely vat dyed sample as well as that ofthe sample that has been both vat dyed and Washed are then determined(after the samples being tested are conditioned for seventy-two hours atthe particular temperature and relative humidity conditions involved ineach of the tests) by tautly connecting a'web-like sample of the yarnbetween two electrodes, each of which are 9 centimeters long spacedparallel 13 centimeters apart, and across which-there is applied a 900volt direct current potential. For purposes of comparison, the volumeresistivities of cotton, wool and an unmodified polyacrylonitrile fiber(obtained in the same Way as the copolymer-containing fiber but withouthaving the graft copolymeric additament incorporated therein) are alsotested in the indicated manner flong with the graft copoiymer-containingsynthetic fiber product in accordance with the present invention.

The results are set forth in the following tabulation which indicatesthe volume resistivities obtained at various relative humidities (RH) at23 C. of each of the samples tested.

Table 1.--V0lume Resistivities of Various Fiber Samples Compared toPolyacrylonizrile Fibers Impregnated With Graft Copolymer of SodiumStyrene Sulfonate 0n PVM As is apparent in the foregoing, the graftcopolymercontaining samples, even after being vat dyed, and dyed andseverely washed, have electrical conductance properties much superiorto'ordinary polyacrylonitrile and 5 only slightly poorer than cotton. Atthe same time, the physical properties of the copolymercontaining fibersare excellent, being about equal to those of the unmodifiedpolyacrylonitrile fiber.

ILLUSTRATION C Following the procedure of Illustration A and using thesame monomeric diester as therein described, a graft copolymer productis prepared from the following charge:

Monomeric diester from Illustration A grams 1.1 PVM (as in illustrationA) do 2.6 Water ml 19.0 Potassium persulfate grams 0.02

The pH of the reaction mass is adjusted to about 9.5 with sodiumhydroxide. The graft copolymerization is carried out for 16 hours at 50C. A colorless, waterinsoluble graft copolymer product is obtained thatis easily dispersible in water in order to form aqueous dispersionssuitable for impregnation of acrylonitrile polymer fibers in accordanceWith the technique set forth in Illustration B. About 84.3 percent ofthe monomeric diester is found to be converted to graft copolymerproduct. The product graft copolymer is found to contain about 74percent of PVM and about 26 percent of graft copolymerized diestersubstituents. When the graft copolymer product is incorporated inpolyacrylonitrile fibers in the manner set forth in the second example,it is found to be an excellent dye-assisting additive and permanentantistatic agent for the fibers. The graft copolymer-containing fibershas good dye-receptivity, excellently loW static characteristics andexcellent physical properties.

ILLUSTRATION D Using the same apparatus as described in Illustration A,a monomeric dimethacrylate ester of a pelyglycol is prepared from thefollowing charge.

Polyglycol having average molecular Weight of about 6000 and of thestructural formula:

HO(CH CH O) CH CH OH grams 1000 Methyl methacrylate do 200 Para-toluenesulfonic acid do 20 Hydroquinone do 10 The charged ingredients in thereactor are heated to a temperature of about 120 C. The fractionatingcolumn on the apparatus is operated at total reflux until the overheadtemperature comes to about 65 C. After this, distillate is removed fromthe column at 65-68 C. for a 4- hour period. The excess methylmethacrylate is then removed under vacuum (2 mm. Hg absolute) for 2hours. One liter of Water is then added to the monomer-containingreaction mass and the polymeric solids filtered out. The resultingaqueous monomer solution is then passed through a bed of Dowex 1 ionexchange resin to remove the hydroquinone polymerization inhibitor. Theuninhibited aqueous monomer Solution is then stored at about 30 C. untilready for use.

About 37.4 grams of the monomeric dimethacrylate ester of the polyglycolis then mixed with about 87.0 grams of PVM having a Fikentscher K-valueof about 45; 499 grams of water; and 0.4 gram of azobisisobutyronitrile.The charge, having a pH of about 6, is graft copolymerized in the mannerset forth in the preceding illustrations over a 24-hoiu' period at 50 C.under nitrogen. At the end of this period, more than 50 percent of themonomer is converted to a graft copolymer product which is Waterinsoluble, but which can be easily dispersed in water by simplemechanical means. The graft copolymer product is found to contain about18 percent of the graft copolymerized dimethacrylate polyglycol diesterunits and about 82 percent of PVM. It is found to be an excellent dyeadditive and permanent antistatic agent for acrylonitrile polymer fiberswhen it is incorporated in them in the manner set forth in the secondillustration. The graft cohours at a temperature of 50" 0.:

7 polymer-containing fibers have good dye-receptivity, excellent staticcharacteristics, satisfactory stability and suitable physicalproperties.

ILLUSTRATION E The general procedure of Illustration D is employed toprepare a mixed graft copolymer from the following charge which ispolymerized under nitrogen for about 18 Grams Monomeric diester (fromIllustration D) 34.0 Sodium styrene sulfonate 1.1 PVM (FikentscherK-value of 45) 82.0 Water 468.5 Potassium persulfate 0.8

Conversion of the monomers to graft copolymer product is found to beabout 90 percent. The graft copolymer product is found to contain about27 percent of graft copolymerized polyglycol diester units;.about 1percent of graft copolymerized sodium styrene sulfonate units; and about72 percent of the PVM backbone substrate. As in the foregoingillustrations, the graft copolymer product is found to be an excellentdye-assisting additive, stabilizer and permanent anti-static agent foracrylonitrile polymer fibers when it is incorporated in them accordingto the manner set forth in the second illustration. The graftcopolymer-containing fibers have very good acceptance of any of a widevariety of dyestuffs, extremely low static characteristics and suitablestability and physical properties.

ILLUSTRATION F An excellent graft copolymer product well suited forpurposes of the present invention is made by polymerizing about 6 gramsof tetramethyleneglycoldimethacrylate and 6 grams of K-30 PVM in 48grams of Water at 50 C. under nitrogen for 16 hours using 0.12 grampotassium persulfate as a catalyst, with the reaction mass having a pHof about 3. Conversion to graft copolymer product (obtained as a soft,White insoluble gel) is about 91 percent.

Excellent results may also be obtained when the foregoing is repeated toprepare graft copolymer additives from other N-vinyl-3-morpholiuonepolymer substrates, such as copolymers of VM with N-vinyl-Z-pyrrolidone;N- vinyl piperidone and other vinyl lactam monomers; N-vinyl-2-oxazolidinone; N-vinyl-S-methyl-Z-oxazolidinone;N-vinyl-S-ethyl-2-oxazolidinone; N-vinyl- -oxazinidinone; and otherN-vinyl cyclic carbamate monomers, and so forth, within thecompositional ranges detailed below.

These N-vinyl-3-morpholinone polymers and their preparation arediscussed in U.S. Patents 2,952,668, filed April 16, 1958; 2,946,772,filed February 27, 1958; and 2,948,- 708, filed April 3, 1958; and inthe copending application for US. patent having Serial No. 692,587,filed October 28, 1957, and entitled N-Vinyl-3-Morpholinone Compounds,now U. S. Patent 2,987,509.

Results similar to those set forth in the foregoing can likewise beobtained when the graft copolymer additaments are incorporated inpolyacrylonitrile and other acrylonitrile-polymer fibers to providearticles in accordance with the present invention by blending the graftcopolymer and the fiber-containing acrylonitrile polymer in a spinningcomposition or dope prior to its extrusion into filamentary products byeither Wet spinning or dry spinning techniques. In such instances,incidentally, it may be desirable, in order to secure optimum benefit inthe practice of the invention, to employ relatively larger quantities ofthe graft copolymeric additament than when surface impregnation isperformed so that the presence of effective quantifies of the additamentat or near the peripheral portion of the article is assured.

The monomeric diacrylate and dimethacrylate esters of polyglycols thatare employed for the preparation of the graft copolymers in the practiceof the present invention are, as is indicated in the foregoing, preparedfrom the esterification of polyethylene or polypropylene glycols,mixtures of such polyglycols, or mixed polyethylene-poly-- propylenepolyglycols with acrylic or methacrylic acids, respectively, or methylor ethyl esters or other reactivederivatives of such acids. Thepolyglycols that are employed for the preparation of the difunctionalmonomeric diesters must be double-ended, i.e., have active hydroxylgroups at both ends and not the monoether or similar polyglycols whichhave other non-reactive terminal substitu-- tions. Advantageously, thepolyglycols that are employed for the preparation of the monomers havemolecular weights from about 300 to 9,000, preferably between about 600and 1,200. The monomeric diesters utilized in the practice of thepresent invention may be represented by the generic formula:

wherein Z and G are independently selected from thegroup consisting ofhydrogen and alkyl radicals containing from 1 to about 2 carbon atoms(advantageously being hydrogen or methyl); m is a number having anaverage value from 6 to and n is a number having an averagevalue from 0to about 10, with the limitation that the value of n is less than abouthalf the value of m.

If desired, as has been indicated and demonstrated, the monomericdiesters used in the present invention may be employed in combination ormixture with other varieties of monomers in order to prepare mixed graftcopolymers having specific properties and effects, particularly withrespect to their capability for accepting greater numbers of diversetypes of dyestuffs. For example, the monomeric diacrylate anddimethacrylate esters of the polyglycols generally provide graftcopolymers showing excellent acceptance of acid or direct types ofdyestuffs. However, other varieties of monomers, such as those which mayprovide acidic chemical characteristics in the resulting graft copolymerstructure, may frequently be used with great advantage to enhance thedye-attracting potency of the resulting graft copolymeric additive tobasic dyestuffs.

Thus, it may frequently be an advantage to graft copolymerized mixturesof the monomeric diesters with monomeric, alkenyl group-containing,organic sulfonie acids or derivatives thereof that are selected from thegroup of such compounds (including mixtures thereof) consisting of thoserepresented by the formulae:

Yr Rm 0 11:0 +(CH2) pSO X (sulfoalkylacrylate organic sulfonic acidcompounds) Z (acryloyl taurine homolog compounds) and GH2=C,CH2NH(oH2n-SO3X Z (VI) (aliyl taurine homolog compounds) all wherein X ishydrogen, an aliphatic hydrocarbon radical containing from 1 to 4 carbonatoms or an alkali metal r'on (including sodium, potassium and lithium);Y is hydrogen, chlorine or bromine; R is methyl or ethyl; Z is hydrogenor methyl; m has a numerical value in Whole number increments from to 2;n has a numerical value of 1 to 2; p is 0 or 1 and r has a numericalvalue of 1 to 4.

Besides these specifically illustrated herein, other or- Still others,

are set forth in the following representative, but by no meansexhaustive, list:

Aromatic alkenyl-containing sulfonic acid compounds (Formula II)Para-styrene sulfonic acid Alkenyl sulfonic acid compounds (FormulaIII):

Ethylene sulfonic acid Sodium ethylene sulfonate Potassium ethylenesulfonate Methyl ethylene sulfonate Isopropyl ethylene sulfonatel-propene 3-sulfonic acid l-propene l-sulfonic acid, sodium saltl-propene 2-sulfonic acid, ethyl ester l-butylene 4-sulfonic acid,n-butyl ester l-butylene 3-sulfonic acid Tertiary butylene sulfonic acidSulfoalkylacrylate compounds (Formula IV):

Sulfomethylacrylate Z-sulfoethylacrylate Sulfomethylmethacrylate, sodiumsalt 2-sulfoethylmethacrylate, methyl ester 2-sulfoethylmethacrylate,potassium salt Acryloyl taurine and homolog compounds (Formula V):

N-acryloyl taurine N-acryloyl taurine, sodium salt N-methacryloyltaurine, methyl ester N-methacryloyl taurine, potassium salt N-acryloyltaurine, ethyl ester N-acryloyl-aminomethane sulfonic acidN-methacryloyl-aminomethane. sulfonic acid, sodium salt MethylN-methacryloyl-aminomethane sulfonate Allyl taurine and homologcompounds (Formula VI):

Allyl taurine Allyl taurine, sodium salt Allyl taurine, potassium saltMethallyl taurine Methallyl taurine, methyl ester Methallyl taurine,isopropyl ester N-allyl-aminomethane sulfonic acid SodiumN-allyl-aminomethane sulfonate Lithium N-methallyl-aminomethanesulfonate n-Butyl N-allyl-aminomethane sulfonate TheN-vinyl-3-morpholinone polymers that are utilized as preformedsubstrates in the preparation of the graft copolymeric additaments ofthe present invention have, as an essential constituent of theirpolymeric structure, characterizing proportions of the recurring group f-CHOH As has been. indicated, copolymers of N-vinyl-3-morpholinone mayalso be employed. Thus, copolymers of N-vinyl-3-morpholinone withvarious homologous alkyl ring-substituted N-vinyl-3-morpholinonemonomers may be utilized, such as copolymers'of N-vinyl-3-morpholinonewith N-vinyl-5-methyl-3-morpholinone, N-vinyl-5-ethyl-3- morpholinone,and the like. Copolymers of N-vinyl-3- morpholinone with various V-vinyllactam polymers, such as N-vinyl pyrrolidone, N-vinyl-piperidone,N-vinyl caprolactam, N-vinyl-S-methyl-2-pyrrolidone and the like mayalso be prepared. Advantages are also achieved with copolymers ofN-vinyl-3-morpholinone and various of the N-vinyl-Z-oxazolidinonemonomers, such as N-vinyl-2- oxazolidinone,N-vinyl-S-methyl-Z-oxazolidinone, N-vinyl- 5-ethyl-2-oxazolidinone,N-vinyl-Z-oxazinidinone, and so forth.

Advantageously, the N-vinyl-3-morpholinone polymer that is used in themanufacture of the graft copolymer product has a Fikentscher K-valuebetween about 5-10 and about and, more advantageously, between about2030 and 60.

Beneficially, as mentioned, the N-vinyl-3-morpholinone polymer that isutilized is a water-soluble material. In cases whereN-vinyl-S-morpholinone copolymers are employed that tend towater-insolubility with decreasing proportions of N-vinyl-3-morpholinonein the copolymer molecule (as is the case with copolymers of N-vinyl-3-morpholinone and N-vinyl-S-methyl-2-oxazolidinone), it is generally mostdesirable for the copolymer to contain at least about 40 weight percentof the N-vinyl-3rnorpholinone polymerized therein. This avoids Workingwith a product that may have a cloud (or precipitation) point in wateror other aqueous solution beneath the boil.

The graft copolymers of the present invention may generally be preparedby methods of polymerization, such as those which have been demonstratedin the foregoing i1- lustrative examples, that employ suchpolymerization cata lysts as persulfates, organic and inorganic peroxideand azo type material-s in quantities that are conventional for suchuses. The graft copolymers may oftentimes be prepared by polymerizingthe monomeric constituent onto the preformed VM substrate under theinfluence of actinic radiations, such as ultra-violet light, or highenergy irradiation, such as by means of X-rays, electron beams,emissions from radioactive sources and the like, or simply by heating orevaporating the monomer and polymer-containing polymerization mixture.The graft copolymers maybe prepared in both aqueous and organic solventvehicles using temperatures for the desired polymerization that may varyfrom about room temperature to the boiling point of the polymerizationmixture. It is ordinarily 1 l satisfactory to conduct the reaction at atemperature of about 50 to 80 or 100 C. Usually, depending on thespecific factors that may be'involved, the graft copolymerization may beaccomplished satisfactorily within a time period of about 5 to 60 hours.

The compositions of the graft copolymer can vary within rather widelimits. The content of the monomeric polyglycol diester constituent thatis graft copolymerized on the preformed VM substrate may advantageouslybe between about 20 and 8-0 Weight percent of the resulting graftcopolymer product and, more advantageously, be tween about 30 and 50weight percent. In many cases, especially to secure optimumdye-receptivity, near equivalent or about commensurate or equal weightproportions of the VM polymer and the monomeric diester constituentgraft copolymerized thereto may be employed with benefit in the graftcopolymeric additaments. When mixtures of the monomeric diesters withmonomeric organic sulfonic acids are employed to prepare mixed graftcopolymer products on the VM polymer, it is desirable for the totalquantity of graft copolymerized constituents on the preformed VM polymersubstrate to remain within the above-stated ranges (i.e., from 20 or 30to 50 or 80 weight percent) with from about 10 to 90 mole percent of thegraft copolymerized substituents being comprised of graft copolymerizedmonomeric polyglycol diester units and, more advantageously, from 3:0 to60 mole per cent of the graft copolymerized constituents consisting ofpolymerized monomeric polyglycol diester units with the balance beingpolymerized units of monomeric organic sulfonic acid compound upon the80 to 20 weight percent of the VM polymer that is contained in the graftcopolymer structure.

The graft copolymers upon PVM and other VM polymers of the polyglycoldiacrylate or dimethacrylate monomers are wax-like solids whoseproperties depend to some extent on the molecular weight of theprecursor polyglycols from which the monomeric diesters are derived. Allof the graft copolymer products are cross-linked, water-insolublematerials which, as mentioned and illustrated, may be dispersed readilyin water or organic solvents.

The polymerization system that is employed for the preparation of thegraft copolymers used in the present invention may consist of as much as50 weight percent of the monomers to be polymerized in the aqueous orother medium. The amount of polymerizable constituents that are providedin the copolymerization system may be influenced somewhat by the mannerin which it is intended to incorporate the product in the syntheticpolymer compositions in order to provide the compositions of theinvention.

If, for example, it is intended to incorporate the graft copolymerproducts by blending into a fiber-forming composition prior to itsfabrication into shaped articles, the graft copolymerization system may,if desired, contain about equal proportions by weight of the chargedpolymerizable constituents and the polymerization medium which,preferably, is miscible with and tolerable in the spinning solutionsolvent being used. In such cases, the graft copolymer product mayordinarily be obtained as an easily dispersed gel that, after beingdried and isolated from unreacted monomer, may readily be directlyincorporated in the fiber-forming composition.

If the incorporation of the graft copolymeric additament in afiber-forming composition is to be achieved by impregnation therewith ofan already-formed shaped article of the composition, it may be desirableto effect the polymerization so as to directly form the polymerizationsystem as a suitable applicating emulsion or suspension of the graftcopolymeric product. For such purposes, the polymerization system may beprepared to contain as little as 2 or 10 percent by weight of thepolymerizable monomeric and polymeric ingredients. Preferably, such apolymerization maybe conducted under the influence of vigorous agitationto facilitate preparation of an emulsified or thoroughly dispersedproduct. It may also be beneficial under such circumstances although'itis usually not necessary to incorporate a dispersant or emulsifyingagent in the polymerization system to facilitate obtaining a stable andhomogeneous emulsified product. method for preparing the graftcopolymeric additaments that are employed in the present invention maybe especially appropriate when they are intended to be applied toacrylonitrile polymer fibers and the. like that are derived fromaquagels in the course of their manufacture, such as the acrylonitrilepolymer fibers that are wet spun from aqueous saline solutions of thefiber-forming polymer.

In such instances, as has been demonstrated, the emulsified,water-insoluble, graft copolymeric additameuts may be impregnated intothe fiber while it is in a swollen or gel condition, as an acrylonitrilepolymer fiber in an aquagel condition, in order to obtain the desiredcopolymer-com raining product. I

In this connection, when it is desired to blend the graft copolymericadditament in a synthetic polymer fiberforming solution prior to itsextrusion, such as an aqueous saline acrylonitrile polymer solution, thewater-insoluble graft copolymer maybe physically reduced by comminutionto a sufficiently fine state to permit its dispersion in spitunablecondition throughout the blended spinning solution in the event that itis otherwise insoluble in the solvent. While this may be accomplished bydiverse techniques, it is generally advantageous to comminute the graftcopolymer in the presence of the non-dissolving solvent, such as anaqueous saline solvent for polyacrylonitrile, to form a stablesuspension that may be more conveniently blended with the spinningsolution of the synthetic polymer, such as an aqueous, salineacrylonitrile polymer spinning solution.

Thus, if the aqueous saline solvent for polyacrylonitrile that is beingemployed is an aqueous solution of zinc chloride or its equivalent thatcontains at least about 55 weight percent and preferably about 60 weightpercent of dissolved zinc chloride, it may be advantageous to comminutethe graft copolymeric additament while it is in a mixture with thesaline solvent solution that contains between about 5 and 10 weightpercent of the copolymer. Analogous procedures may be employed whenother solvents are involved. Ball or rod mills or other attritionapparatus may be employed satisfactorily for the comminution. It isgenerally beneficial under such circumstances to avoid the use of ballsor rods that are made of metal since they may contaminate the product,especially when aqueous saline solvents are utilized. Porcelain or otherceramic parts may usually be employed with advantage. A stablesuspension of the graft copolymeric additament in the acrylonitrilepolymer solvent that is suitable for blending in the spinning solutionof the acrylonitrile poly mer to provide a spinnable composition mayusually be obtained by milling the mixture of graft copolymericadditament and solvent for an extended period that may exceed hours. Thesuspension that is thereby obtained may then be directly blended in theproper proportions with the acrylonitrile polymer spinning solution toprovide a composition in accordance with the present invention.

If desired, the copolymer-containing acrylonitrile polymer compositionsmay comprise as much as 20 or more Weight percent of the graftcopolymeric additament, based on the weight of the composition. Usually,however, suitable properties and characteristics and betterfiberforrning properties in a given composition may be achieved whenlesser proportions of the copolymeric additament are incorporatedtherein. An appreciable improvement in dye-receptivity, antistaticproperties and stability may frequently be obtained when a quantity ofthe copolymeric additament that is as small as 3 (and even as low as 1or less) percent by weight is employed. Advantageously, an amountbetween about 3 and 15 percent by weight of the copolymeric additamentmay thus Such a 13 be utilized in the composition. Greater advantagesmay often accrue when the amount of the copoiymeric additament that isincorporated in the composition is in the neighborhood of 610 percent byweight, based on the weight of the composition.

As has been indicated, the graft copolymeric additaments may beincorporated in the acrylonitrile polymer compositions according tovarious techniques. Thus, for example, the copolymeric additament andthe acrylonitrile polymer may be directly blended in order to providethe composition which, incidentally, may be used for any desiredfabrication purpose in addition to fiber-forming and the like.Beneficially, the polymers may be comminuted, either separately or incombination, before being intimately blended together by mechanical orother means. The blended polymers may be prepared into suitablefiberforming systems by dissolving or otherwise dispersing them in asuitable liquid medium. Or, the compositions may be provided infiber-forming system by sequentially dispersing the polymers in anydesired order in a suitable medium, as by incorporating the graftcopolymeric additament in a prepared acrylonitrile polymer spinningsolution, dope or the like.

As is evident from the illustrative examples heretofore included, ahighly advantageous technique for providing the compositions,particularly when acrylonitrile polymer fiber products are involved, isto apply or impregnate the copolymeric additament from an aqueousdispersion thereof to a shaped acrylonitrile polymer article that is inan aquagel condition in a known manner. Thus, an acrylonitrile polymerfilamentary article that has been spun from an aqueous saline spinningsolution may be conveniently passed, after its coagulation and while itis in an aquagel condition, through a water bath containing thedissolved graft copolymeric additament in order to impregnate thefilament with the graft copolymer and provide a composition and anarticle in accordance with the invention.

In addition, it is oftentimes possible for in situ polymerizationtechniques to be accomplished and relied upon to provide the graftcopolymeric additarnent in the acrylonitrile polymers in eitherfabricated or unfabricated form.

The compositions of the invention may advantageously be utilized in orwith fiber-forming systems of any desired type in order to providefibers and the like according to procedures and techniques that areconventionally employed for such purposes in the preparation of fibersand such related shaped articles as filaments, strands, yarns, tows,threads, cords and other funicular structures, ribbons, tapes, films,foils, sheets and the like which may be manufactured from syntheticpolymeric materials. It is irequently desirable to employ concentratedsolutions of salts or mixtures of salts as the dispersing or dissolvingmedia for such purposes. Such solutions may, as has been indicated,contain at least about 55 percent by weight, based on the weight of thesolution, of zinc chloride or other known saline solvents for thepolymer. Acrylonitrile polymer fiber products that are spun from salinefiber-forming systems may, by way of further illustration, be coagulatedin more dilute saline solutions of a like or similar nature and may thenbe processed after coagulating according to conventional techniques ofwashing, stretching, drying, finishing and the like vw'th themodification of the present invention being accomplished prior orsubsequent to the spinning as may be desired and suitable in particularinstances.

The acrylonitrile polymer fiber products in accordance with the presentinvention (one of which is schematically illustrated in the sole figureof the accompanying drawing) have excellent physical properties andother desirable characteristics for a textile material and have a highcapacity for and are readily and satisfactorily dyeable to deep andlevel shades with any of a wide variety of dyestuffs. For example,.theymay be easily and successfully dyedaccording to conventional proceduresusing acid, vat, acetate, direct, naphthol and sulfur dyes.

Such dyestuffs, by way of didactic illustration, as Calcocid AlizarineViolet (Colour Index 61710, formerly Colour Index 1080), SulfantitreneRed 3B (Colour Index Vat Violet 2), Amacel Scarlet GB (Colour IndexDirect Red 1-also known as Amacel Scarlet BS, and having AmericanPrototype Number 244), Calcodur Pink 2BL (Colour Index 353, also morerecently, Colour Index Direct Red 75), Naphthol ASMX (Colour Index35527), Fast Red TRN Salt (Colour Index Azoic Diazo Component 11), andImmedial Bordeaux G (Colour Index Sulfur Brown 12) may advantageously beemployed for such purposes.

Other dyestuffs, by way of further illustration, that may be utilizedbeneficially on the graft copolymer-containing, polymer blended fiberproducts of the invention include such direct cotton dyes as ChlorantineFast Green SBLL (Colour Index Direct Green 27), Chlorantine Fast Red 7B(Colour Index Direct Red 81), Pontamine Green GX Conc. 125 percent(Colour Index Direct Green 6), Calcomine Black EXN conc. (Colour IndexDirect Black 38), Niagara Blue NR (Colour Index Direct Blue 151) andErie Fast Scarlet. 4BA Colour Index Direct Red 24); such acid dyes asAnthraquinone Green GN (Colour Index Acid Green 25), Sulfonine Brown 2R(Colour Index Acid Orange 51), Sulfonine Yellow 2G (Colour Index AcidYellow 40), Xylene Milling Black 23 (Colour Index Acid Black 26A),Xylene Milling Blue FF (Colour Index Acid Blue 61), Xylene Fast Rubine3GP PAT (Colour Index Acid Red 57), Calcocid Navy Blue R Conc. (ColourIndex Acid Blue 120), Calcocid Fast Blue BL (Colour Index Fast Blue 59),Calcocid Milling Red 3R (Colour Index Acid Red 151), Alizarine LevellingBlue 2R (Colour Index Acid Blue 51), Amacid Azo Yellow G Extra (ColourIndex Acid Yellow 63; such mordant-acid dyes as Alizarine Light Green GS(Colour Index Acid Green 25); such basic dyes as Brilliant GreenCrystals (Colour Index Basic Green 1) and Rhodamine B Extra S (ColourIndex Vat Blue 35); such vat dyestuffs as Midland Vat Blue R Powder(Colour Index Vat Blue 35), SulranthreneBrown G Paste (Colour Index VatBrown 5), Sulfanthrene Blue 2B Dbl. paste (Colour Index Vat Blue 5), andSulfanthrene Red 3B paste (Colour Index Vat Violet 2); various solublevat dyestufis; such acetate dyes as Celliton Fast Brown BRA Extra CF(Colour Index Dispersed Orange 5), Celliton Fast Rubine BA CF (ColourIndex Dispersed Red 13), Artisil Direct Red 3131 and Celanthrene Red 3BNConc. (Both Colour Index Dispersed Red 15), Celanthrene Pure Blue BRS400 percent (Colour Index Dispersed Blue 1) and Acetamine Yellow N(Colour Index Dispersed Yellow 32); B-

Naphthol 2-chloro-4-nitroaniiine, an azoic dye; such sulfur dyes asKatigen Brilliant Blue GGS High Conc. (Colour Index Sulf. Blue 9) andIndo Carbon CLGS (Colour Index Sulf. Blue 6); and various premetallizeddyestuffs.

The dyed products are generally lightfast and stable to heat and arewell imbued with a resistance to crocking. In addition, the dyedproducts exhibit good washfastness and retain the dye-assistingpolymeric additament in a substantially permanent manner despiterepeated exposure and subjection to washing, laundering and dry cleaningtreatments.

What is claimed is:

1. Graft copolymer comprising between about 20 and about weight percentof (a) a monomeric polyfunctional diester of a polyglycol having theformula:

average value from 6 to and n is a number having an average value from 0to 10; with the limitation that the value of n is less than about halfof the value of m; and

15 (b) from about 80'to about 20 weight percent of a polymer of amonoethylenically unsaturated monomeric material containing at leastabout 10 weight percent of N-vinyl-S-morpholinone.

2. The graft copolymer of claim 1, containing in the polymer moleculebetween about 30 and about 50 weight percent of said monomer graftcopolymerized on said N-vinyl-3-morpholinone polymer.

3. The graft copolymer of claim 1, wherein said polymer 7 is,poly-N-vinyl-3-morphoiinone.

4. Graft copolymer comprising between about 26 and about 80 weightpercent of (a) a mixture of monomers consisting of from about 10 toabout 90 mole percent of 1) a monomeric diester of a polyglycol of theformula:

CH =CZC-(0C H V oc n ooc--oc- -(:H (I) wherein Z and G are independentlyselected from the group consisting of hydrogen and alkyl radicalscontain- .ing from 1 to 2 carbon atoms; in is a number having an averagevalue from 6 to 100; and n is a number having an average value from 0 towith the limitation that the value of n is less than about half of thevalue of m; and (2) from about 90 to about 10 mole percent of at leastone monomeric, alkenyl group-containing organic sulfonic acid compoundselected from the group consisting of those represented by the formulae:

all wherein X is selected from the group consisting of hydrogen,aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms andalkali metals; Y is selected from the group consisting of hydrogen,chlorine and bromine; R is selected from the group consisting of methyland ethyl; Z is selected from the group consisting of hydrogen andmethyl, m is an integer from 0 to 2; n is an integer from 1 to 2; and pis an integer from 0 to 1; and r is an integer from 1 to 4; and (b) fromabout 80 to about 20 weight percent of a polymer of a monoethylenicallyunsaturated monomeric material containing at least about 10 weightpercent of N-viny1-3-morpholinone.

5. Method for the preparation of a graft copolymer which comprisespolymerizing between about 20 and about 80 weight percent, based onresulting graft copolymer weight, of a monomeric diester of a polyglycolhaving the formula:

wherein Z and G are independently selected from the group consisting ofhydrogen and alkyl radicals containing from 1 to 2 carbon atoms; m is anumber having an average value from 6 to 100; and n is a number havingan average value from 0 to 10; with the limitation that the value of nis less than about half of the value of m; with between about 80 andabout 20 Weight percent of a polymer of a monoethylenically unsaturatedmonomeric material containing at least about 10 weight percent ofN-vinyl-3-morpholinone.

6. Method for the preparation of a graft copolymer which comprisespolymerizing between about 20 and In about weight percent, based onresulting graft copolymer weight, of (a) a mixture of monomersconsisting of from about 10 to about mole percent of (1) a monomericdiester of a polyglycol of the formula:

wherein Z'and G are independently selected from the group consisting ofhydrogen and alkyl radicals containing from 1 to 2 carbon atoms; In is anumber having an average value from 6 to and n is a number having anaverage value from 0 to 10; with the limitationtthat the value of n isless than about half of the value of m; and (2) from about 90 to 10 molepercent of at least one alkenyl group-containing organic sulfonic acidselected from the group consisting of those having the formulae:

all wherein X is selected from the group consisting of hydrogen,aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms andalkali metals; Y is selected from the group consisting of hydrogen,chlorine and bromine; R is selected from the group consisting of methyland ethyl; Z is selected from the group consisting of hydrogen andmethyl, m is an integer from 0 to 2; n is an integer from 1 to 2; and pis an integer from 0 to 1; and r is an integer from 1 to 4; with (b)between about 80 and about 20 weight percent of a polymer of amonoethylenically unsaturated monomeric material containing at leastabout 10 Weight percent of N-vinyl-B-morpholinone.

7. Composition comprising a major proportion of at least about 80 weightpercent, based on composition weight, of (A) a fiber forming polymer ofan ethylenically unsaturated monomeric material containing at leastabout 80 weight percent of acrylonitrile, and (B) a minor proportion ofup to about 20 weight percent, based on composition weight, of a graftcopolymer of (a) between about 20 and about 80 weight percent of amonomeric diester of a polyglycol having the formula:

wherein Z and G are independently selected from the group consisting ofhydrogen and alkyl radicals containing from 1 to 2 carbon atoms; m is anumber having an average value from 6 to 100; and n is a number havingan average value from 0 to 10; with the limitation that the value ofn isless than about half of the value of m; and (b) from about 80 to about20 weight percent of a polymer of a monoethylenically unsaturatedmonomeric material containing at least about 10 weight percent ofN-vinyl-3-morpholinone.

8. The composition of claim 7 containing between about 4 and about 15weight percent, based on composition weight, of said graft copolymer.

9. The composition of claim 7, wherein component (B) is a graftcopolymer of a monomer of said Formula I wherein m is 2 and n is 0 and Gand Z are both methyl and poly-N-vinyl-3-morpholinone.

10. The composition of claim 7, wherein component (B) is a graftcopolymer of a monomer of said Formula I 17 wherein m is 12 and n is andG and Z are both methyl and poly-N-vinyl-3-morpholinone.

11. The composition of claim 7, wherein component (B) is a graftcopolymer of a monomer of said Formula I wherein m is and n is 3 and Gand Z are both methyl and poly-N-vinyl-3-morpholinone.

12. The composition of claim 7, wherein the acrylonitrile polymer ispolyacrylonitrile.

13. The composition of claim 7, dispersed in a solvent forpolyacrylonitrile.

14. A filamentary shaped article comprised of the composition of claim7.

15. Composition comprising a major proportion of at least about 80weight percent, based on composition weight of (A) a fiber formingpolymer of an ethylenically unsaturated monomeric material containing atleast about 80 weight percent of acrylonitrile, and (B) a minorproportion of up to about weight percent, based on composition weight,of a graft copolymer of (a) between about 20 and about 80 weight percentof a mixture of monomers consisting of 1) from about 10 to about 90 molepercent of a monomeric diester of a polyglycol of the formula:

wherein Z and G are independently selected from the group consisting ofhydrogen and alkyl radicals containing from 1 to 2 carbon atoms; m is anumber having an average value from 6 to 100; and n is a number havingan average value from 0 to 10; with the limitation that the value of nis less than about half of the value of m; and (2) from about 90 toabout 10 mole percent of at least one monomeric alkenyl group-containingorganic sulfonic acid compound selected from the group consisting ofthose having the formulae:

all wherein X is selected from the group consisting of hydrogen,aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms andalkali metals; Y is selected from the group consisting of hydrogen,chlorine and bromine; R is selected from the group consisting of methyland ethyl; Z is selected from the group consisting of hydrogen andmethyl, m is an integer from 0 to 2; n is an integer from 1 to 2; and pis an integer from O to 1; and r is an integer from 1 to 4; and (b) fromabout 80 to about 20 weight percent of a polymer of a monoethylenicallyunsaturated monomeric material containing at least about 10 weightpercent of N-vinyl-3 -morpholinone.

16. Method for the preparation of a dye-receptive, antistatic, stable tolight and heat, synthetic, linear, hydrophobic polymer composition Whichcomprises immersing an aquagel of a fiber forming polymer of anethylenically unsaturated monomeric material containing at least about80 weight percent of acrylonitrile in the form of a shaped article intoa dispersion of a graft copolymer of (a) between about 20 and about 80weight percent of a monomeric diester of a polyglycol of the vformula:

OOC-GC=CH (I) wherein Z and G are independently selected from the groupconsisting of hydrogen and alkyl radicals containing from 1 to 2 carbonatoms; m is a number having an average value from 6 to 100; and n is anumber having an average value from 0 to 10; with the limitation thatthe value of n is less than about half of the value of m; and (b) fromabout to about 20 Weight percent of a polymer of a monoethylenicallyunsaturated monomeric material containing at least about 10 weightpercent of N-vinyl-3-morpholinone, until between about 2 and about 2i)weight percent of said graft copolymer, based on resulting drycomposition weight, is incorporated in said aquagel; and drying saidgraft copolymer-containing aquagel to convert it from the aquagelcondition to a finished shaped article form.

17. Method for the preparation of a dye-receptive, antistatic, stable tolight and heat, synthetic, linear hydrophobic polymer composition whichcomprises immersing an aquagel of a fiber forming polymer of anethylenically unsaturated monomeric material containing at least about80 weight percent of acrylonitrile in the form of a shaped article intoa dispersion of a graft copolymer of (a) between about 20 and about 80weight percent of a mixture of monomers consisting of (1) from about 10to about mole percent of a monomeric diester of a polyglycol of theformula:

wherein Z and G are independently selected from the group consisting ofhydrogen and alkyl radicals containing from 1 to 2 carbon atoms; m is anumber having an average value from 6 to and n is a number having anaverage value from O to 10; with the limitation that the value of n isless than about half of the value of m; and (2) from about 90 to about10 mole percent of at least one monomeric alkenyl group-containingorganic sulfonic acid compound selected from the group consisting ofthose having the formulae:

all wherein X is selected vfrom the group consisting of hydrogen,aliphatic hydrocarbon radicals containing from 1 to 4 carbon atoms andalkali metals; Y is selected from the group consisting of hydrogen,chlorine and bromine; R is selected from the group consisting of methyland ethyl; Z is selected from the group consisting of hydrogen andmethyl; m is an integer from 0 to 2; n is an integer from 1 to 2; and pis an integer from 0 to 1; and r is an integer from 1 to 4; and (b) fromabout 80 to about 20 weight percent of a polymer of monoethylenicallyunsaturated monomeric material containing at least about 10 weightpercent of N-vinyl-3-morpholinone, until between about 2 and about 20weight percent of said graft copolymer based on resulting drycomposition weight, is incorporated in said aquagel; and drying saidgraft copolytrier-containing aquagel to convert it from the aquagelcondition to a finished shaped article form.

References Cited in the file of this patent UNITED STATES PATENTS2,614,289 Cresswell et al Oct. 21, 1952

15. COMPOSITION COMPRISING A MAJOR PROPORTION OF AT LEAST ABOUT 80WEIGHT PERCENT, BASED ON COMPOSITION WEIGHT OF (A) A FIBER FORMINGPOLYMER OF AN ETHYLENICALLY UNSATURATED MONOMERIC MATERIAL CONTAINING ATLEAST ABOUT 80 WEIGHT PERCENT OF ACRYLONITRILE, AND (B) A MINORPROPORTION OF UP TO ABOUT 20 WEIGHT PERCENT, BASED ON COMPOSITIONWEIGHT, OF A GRAFT COPOLYMER OF (A) BETWEEN ABOUT 20 AND ABOUT 80 WEIGHTPERCENT OF A MIXTURE OF MONOMERS CONSISTING OF (1) FROM ABOUT 10 TOABOUT 90 MOLE PERCENT OF A MONOMERIC DIESTER OF A POLYGLYCOL OF THEFORMULA: